EP1554413B1 - Method for producing semiconducting devices - Google Patents

Method for producing semiconducting devices Download PDF

Info

Publication number
EP1554413B1
EP1554413B1 EP03750232.5A EP03750232A EP1554413B1 EP 1554413 B1 EP1554413 B1 EP 1554413B1 EP 03750232 A EP03750232 A EP 03750232A EP 1554413 B1 EP1554413 B1 EP 1554413B1
Authority
EP
European Patent Office
Prior art keywords
layer
dosing
deposition
doped
contamination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03750232.5A
Other languages
German (de)
French (fr)
Other versions
EP1554413A2 (en
Inventor
Ulrich Kroll
Cédric BUCHER
Jacques Schmitt
Markus Poppeller
Christoph Hollenstein
Juliette Ballutaud
Alan Howling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TEL Solar AG
Original Assignee
TEL Solar AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TEL Solar AG filed Critical TEL Solar AG
Publication of EP1554413A2 publication Critical patent/EP1554413A2/en
Application granted granted Critical
Publication of EP1554413B1 publication Critical patent/EP1554413B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
    • H10P14/2901—Materials
    • H10P14/2921—Materials being crystalline insulating materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/122—Active materials comprising only Group IV materials
    • H10F77/1223—Active materials comprising only Group IV materials characterised by the dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3241—Materials thereof being conductive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
    • H10P14/3408—Silicon carbide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3438—Doping during depositing
    • H10P14/3441—Conductivity type
    • H10P14/3444—P-type
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/38—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by treatments done after the formation of the materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
    • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
    • H10P32/15—Diffusion of dopants within, into or out of semiconductor bodies or layers from the substrate during epitaxy, e.g. autodoping; Preventing or using autodoping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates in general to the domain of semiconductor films based on silicon technology. It concerns, more particularly, a method for producing silicon junctions, doped or not, which can be used, for example, in solar cells. It also concerns any other semi-conducting devices obtained by such a method.
  • Amorphous or microcrystalline silicon solar cells are made of multilayer systems where semiconducting material with certain electronical and physical properties is deposited, layer by layer, on a substrate.
  • n-layers and p-layers are doped with other elements to achieve desired properties, such as electrical conductivity. More precisely :
  • boron is used as the doping agent of the p-layers and phosphorus as the doping agent of the n-layers.
  • Silicon solar cells manufacturers use either single-chamber or multi-chamber reactors to produce commercial photovoltaic (PV) modules.
  • PV photovoltaic
  • Plasma deposition of silicon solar cells in a single-chamber reactor leads to considerable simplifications and reduced costs as compared to multi-chamber processes.
  • the subsequent deposition of the i-layer on the p-layer may cause boron recycling from the reactor walls and from the deposited p-layer.
  • boron will contaminate the i-layer at the critical p-i interface and thereby weaken the strength of the electrical field in the i-layer close to p-i interface. This provokes a less efficient carrier separation just in this zone and leads to a reduced collection efficiency in the solar cell and thereby to a deterioration of the cell performance.
  • an interesting solution would be to combine a low cost-single chamber reactor with a process scheme able to suppress the boron or phosphorus cross-contamination.
  • the object of the present invention is to provide a method for producing semiconductors with a particular application in solar cells, avoiding cross-contamination by doping agents and exempt of disadvantages above mentioned.
  • the invention concerns a method for producing a semi-conducting device comprising at least a layer doped with a doping agent and a layer of another type deposited on said doped layer in a single reaction chamber.
  • the deposition steps of said layers are separated by an operation for avoiding the contamination by the doping agent of said another layer.
  • the operation comprises a dosing of the reaction chamber with a compound able to react with the doping agent.
  • the contamination avoiding operation comprises a dosing of the reaction chamber with a vapour or gas comprising water, methanol, isopropanol or another alcohol.
  • the contamination avoiding operation comprises a dosing of the reaction chamber with a vapour or gas comprising ammonia, hydrazine or volatile organic amines.
  • a boron doped p-i-n junction i.e. a semiconductor device comprising respective p, i and n layers successively deposited on a suitable substrate providing the base of a solar cell.
  • the three layers are deposited in a manner well known by a person skilled in the art but, according to the invention, the method comprises an important supplementary step.
  • Figure 1 shows the reactor used to produce such a semi-conducting device. Basically, it comprises :
  • a substrate 15 for example a glass/TCO substrate of the type Asahi U, based on SnO 2 :F (glass coated with fluorine doped Sn02), is being arranged in the inner chamber 12.
  • the above described installation is preferably adapted from the industrial KAITM-S reactor of Unaxis Displays in order to constitute a Plasma Enhanced Chemical Vapour Deposition (PECVD) system.
  • the typical dimensions of the inner chamber 12 are 50cm width x 60cm length x 2.5cm height.
  • the reacting gas introduced in the reactor through the showerhead 14 are, typically:
  • TMB is particularly well suited, instead of diborane (commonly used) because it has a superior thermal stability in the hot reactor and is reported to cause less contamination.
  • the plasma excitation frequency used is e.g. 40.68 MHz
  • the temperature is 200°C
  • the pressure is kept at 0.3 hPa
  • the power RF is applied at a level of 60 W.
  • the internal surfaces of the reactor and the substrate also are dosed with a vapour or a gas comprising water, methanol or isopropanol or another alcohol.
  • the dosing product is stored in a separate bottle 21 connected, via a valve 22, to the vacuum chamber 10, which is kept at low pressure condition.
  • the valve 22 When the valve 22 is opened, the dosing product starts boiling in the bottle 21 because of the low pressure inside and vapour flushes into the chamber 10.
  • the RF electrode 13 is off.
  • the operation is performed between 100 and 350°C, typically at 200°C and during less than 10 minutes, typically 2 minutes and at 0.05 to 100 hPa.
  • the flow of water vapour has to be sufficient. For example, 90 hPa.sec is a good value. If methanol or isopropanol is used, the flow is generally higher.
  • the i-layer, then the n-layer are deposited in the same reactor.
  • the conditions described above for the p-layer deposition are reused with appropriate reacting gases, as known by a person skilled in the art.
  • the reacting gases used for the deposition of the i-layer are a mix of 75% of silane and 25% of hydrogen
  • the reacting gases used for the deposition of the n-layer are silane, hydrogen and phosphine.
  • the evaluation of the base level boron contamination of the i-layers can be made by Secondary ion Mass Spectroscopy (SIMS) in order to trace the boron concentration depth profile across the p-i interface.
  • SIMS Secondary ion Mass Spectroscopy
  • figure 2 shows, as an example, the boron SIMS profile (depth X from surface in Angstroms versus boron concentration Y in atoms.cm -3 ) of a p-i-p-i sandwich structure deposited on a c-Si wafer. Both p-doped portions 17 and 18 are normally deposited.
  • a first i-layer 19 is deposited on the p-layer 17 without performing any additional treatment.
  • the base level contamination of boron measured in the i-layer 19 is about 10 18 atoms.cm -3 .
  • a second i-layer 20 is deposited on the p-layer 18 portion after the dosing treatment as described above.
  • the base level contamination of boron measured in the i-layer 20 is reduced to about 10 17 atoms.cm -3 , which represents an improvement of one order of magnitude.
  • the boron contamination in the i-layer of a solar p-i-n cell treated according to the invention can also be indirectly detected by performing voltage dependent quantum efficiency measurements as well as monitoring the global cell performance especially the fill factor of the solar cell.
  • the results are substantially the same as those obtained with cells deposited in multi-chamber reactors.
  • an oxygen peak can be observed with a SIMS analysis at the treated p-i interface, meaning that the above described treatment has been used.
  • the amount of oxygen in the peak is higher than 10 19 atoms.cm 3 .
  • the internal surfaces of the reactor are dosed with a vapour or gas comprising ammonia, hydrazine or volatile organic amines.
  • This dosing operation is performed at low pressure conditions (0.05 to 100 hPa), between 100 and 350°C, typically at around 200°C and during less than 10 minutes, typically around to 2 minutes.
  • the flow of gas has to be sufficient.
  • 90 hPa.sec is a good value for ammonia.
  • a short pumping period of less than 5 minutes is also respected before the deposition of the i-layer.
  • a nitrogen peak can be observed with a SIMS analysis at the treated n-i interface, meaning that such a treatment has been used.
  • the amount of nitrogen is higher than 10 19 atoms.cm- 3 .
  • a hydrogen-diluted buffer layer is obtained by PECVD of a mix of 10% silane and 90% hydrogen.
  • the plasma excitation frequency used is 40.68 MHz
  • the temperature is 200°C
  • the pressure is kept at 0.5 hPa and the power RF is applied at a level of 60 W.
  • Such a layer alone has usually already a beneficial effect on the boron cross contamination in the i-layer.
  • the method of the invention offers the advantage to eliminate the boron contamination while working with a single reactor. There is neither wasted pumping time nor loss of time due to transfer of the substrate out of the reactor for a cleaning step nor loss of time for reheating of the substrate which cooled down during the transfer. Moreover, apart from simpler and faster processes the single chamber approach bears the potential of considerably simplified deposition systems as compared to multi-chamber systems. It has to be noted that such methods allow to produce a complete solar cell in only 30 minutes.
  • a person skilled in the art can easily adapt the above described treatments to a n-i-p solar cell in order to avoid phosphorus cross-contamination after the deposition of n-doped layer.
  • the invention can also be applied to any junction based on a p-doped or n-doped layer.
  • the dosing can also be performed by injecting the dosing compound directly in the gas feeding line.

Landscapes

  • Chemical Vapour Deposition (AREA)
  • Photovoltaic Devices (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Description

  • The present invention relates in general to the domain of semiconductor films based on silicon technology. It concerns, more particularly, a method for producing silicon junctions, doped or not, which can be used, for example, in solar cells. It also concerns any other semi-conducting devices obtained by such a method.
  • Amorphous or microcrystalline silicon solar cells are made of multilayer systems where semiconducting material with certain electronical and physical properties is deposited, layer by layer, on a substrate.
  • The n-layers and p-layers are doped with other elements to achieve desired properties, such as electrical conductivity. More precisely :
    • p-doped layers have a surplus of positive charge carriers,
    • n-doped layers have a surplus of negative charge carriers, and
    • i layers are intrinsic.
  • Generally, boron is used as the doping agent of the p-layers and phosphorus as the doping agent of the n-layers.
  • Silicon solar cells manufacturers use either single-chamber or multi-chamber reactors to produce commercial photovoltaic (PV) modules. Plasma deposition of silicon solar cells in a single-chamber reactor leads to considerable simplifications and reduced costs as compared to multi-chamber processes.
  • However, in a single chamber deposition process of a p-i-n solar cell, for example, the subsequent deposition of the i-layer on the p-layer may cause boron recycling from the reactor walls and from the deposited p-layer. As a result, boron will contaminate the i-layer at the critical p-i interface and thereby weaken the strength of the electrical field in the i-layer close to p-i interface. This provokes a less efficient carrier separation just in this zone and leads to a reduced collection efficiency in the solar cell and thereby to a deterioration of the cell performance.
  • For that reason, most silicon p-i-n solar cells modules are, at present, deposited using multi-chamber reactors. Boron cross-contamination by recycling is avoided by simply depositing the p-layer and the i-layer in different chambers. However, the higher investment in multi-chamber systems equipment becomes a drawback particularly in the field of solar cells where costs are a major issue.
  • Similar problems exist with n-i-p solar cells in which phosphorus used to dope the n-layer contaminates the i-layer at the critical n-i interface.
  • Thus, an interesting solution would be to combine a low cost-single chamber reactor with a process scheme able to suppress the boron or phosphorus cross-contamination.
  • Different treatments have been tested with encouraging results, but they still leave open the question of the light-induced degradation of these solar cells, they use expensive gases, they have long treatment durations or are incompatible with large area deposition in industrial reactors.
  • The object of the present invention is to provide a method for producing semiconductors with a particular application in solar cells, avoiding cross-contamination by doping agents and exempt of disadvantages above mentioned.
  • More precisely, in order to achieve these goals, the invention concerns a method for producing a semi-conducting device comprising at least a layer doped with a doping agent and a layer of another type deposited on said doped layer in a single reaction chamber. The deposition steps of said layers are separated by an operation for avoiding the contamination by the doping agent of said another layer.
  • Advantageously, the operation comprises a dosing of the reaction chamber with a compound able to react with the doping agent.
  • According to a first embodiment, the contamination avoiding operation comprises a dosing of the reaction chamber with a vapour or gas comprising water, methanol, isopropanol or another alcohol.
  • According to a second embodiment, the contamination avoiding operation comprises a dosing of the reaction chamber with a vapour or gas comprising ammonia, hydrazine or volatile organic amines.
  • Other characteristics of the invention will be shown in the description below, made with regard to the attached drawing, where:
    • figure 1 shows the reactor used for the implementation of the method, and
    • figure 2 illustrates the effect of the doping agent contamination avoiding operation.
  • The following description is particularly related, as an example, to the production of a boron doped p-i-n junction, i.e. a semiconductor device comprising respective p, i and n layers successively deposited on a suitable substrate providing the base of a solar cell.
  • The three layers are deposited in a manner well known by a person skilled in the art but, according to the invention, the method comprises an important supplementary step.
  • Figure 1 shows the reactor used to produce such a semi-conducting device. Basically, it comprises :
    • a vacuum chamber 10 connected to a vacuum circuit 11,
    • a hot wall inner chamber 12 disposed inside the vacuum chamber 10,
    • a radio-frequency-powered electrode 13 placed inside the inner chamber 12, and
    • a showerhead 14 incorporated within the electrode 13 and connected to different gas feeding lines to introduce appropriate reacting products.
  • A substrate 15, for example a glass/TCO substrate of the type Asahi U, based on SnO2:F (glass coated with fluorine doped Sn02), is being arranged in the inner chamber 12.
  • The above described installation is preferably adapted from the industrial KAI™-S reactor of Unaxis Displays in order to constitute a Plasma Enhanced Chemical Vapour Deposition (PECVD) system. The typical dimensions of the inner chamber 12 are 50cm width x 60cm length x 2.5cm height.
  • For the initial p-layer deposition on substrate 15, the reacting gas introduced in the reactor through the showerhead 14 are, typically:
    • to form the p-layer : silane, methane and hydrogen, and
    • to dope the layer with boron : trimethylboron (TMB).
  • TMB is particularly well suited, instead of diborane (commonly used) because it has a superior thermal stability in the hot reactor and is reported to cause less contamination.
  • To perform the deposition of the p-layer, the plasma excitation frequency used is e.g. 40.68 MHz, the temperature is 200°C, while the pressure is kept at 0.3 hPa, and the power RF is applied at a level of 60 W.
  • Many experiments have suggested that boron introduced in the reactor is not simply present in a gaseous state which could be easily pumped out, but might be physisorbed on the internal reactor surfaces and desorb very slowly after a pumping period.
  • Therefore, according to a first embodiment of the invention, after the deposition of the p-layer and before the deposition of the i-layer, the internal surfaces of the reactor and the substrate also are dosed with a vapour or a gas comprising water, methanol or isopropanol or another alcohol.
  • More precisely, in this example, the dosing product is stored in a separate bottle 21 connected, via a valve 22, to the vacuum chamber 10, which is kept at low pressure condition. When the valve 22 is opened, the dosing product starts boiling in the bottle 21 because of the low pressure inside and vapour flushes into the chamber 10. Of course, the RF electrode 13 is off. The operation is performed between 100 and 350°C, typically at 200°C and during less than 10 minutes, typically 2 minutes and at 0.05 to 100 hPa. The flow of water vapour has to be sufficient. For example, 90 hPa.sec is a good value. If methanol or isopropanol is used, the flow is generally higher.
  • After the dosing operation, a short pumping period of less than 5 minutes, typically around 3 minutes, under similar conditions but without any dosing gas addition, is advantageously respected before the deposition of the i-layer.
  • As a result of the above dosing operation, the boron which was physisorbed on all the internal surfaces of the reactor and of the substrate is transformed into stable chemical compounds unable to desorb. A contamination of the layer which will be later deposited on the p-layer is thus avoided.
  • After this treatment, the i-layer, then the n-layer are deposited in the same reactor. The conditions described above for the p-layer deposition are reused with appropriate reacting gases, as known by a person skilled in the art.
  • As an example, the reacting gases used for the deposition of the i-layer are a mix of 75% of silane and 25% of hydrogen, whereas the reacting gases used for the deposition of the n-layer are silane, hydrogen and phosphine.
  • The evaluation of the base level boron contamination of the i-layers can be made by Secondary ion Mass Spectroscopy (SIMS) in order to trace the boron concentration depth profile across the p-i interface.
  • To illustrate the efficiency of the above-described dosing treatment, figure 2 shows, as an example, the boron SIMS profile (depth X from surface in Angstroms versus boron concentration Y in atoms.cm-3) of a p-i-p-i sandwich structure deposited on a c-Si wafer. Both p-doped portions 17 and 18 are normally deposited.
  • A first i-layer 19 is deposited on the p-layer 17 without performing any additional treatment. The base level contamination of boron measured in the i-layer 19 is about 1018 atoms.cm-3.
  • A second i-layer 20 is deposited on the p-layer 18 portion after the dosing treatment as described above. The base level contamination of boron measured in the i-layer 20 is reduced to about 1017 atoms.cm-3, which represents an improvement of one order of magnitude.
  • The boron contamination in the i-layer of a solar p-i-n cell treated according to the invention can also be indirectly detected by performing voltage dependent quantum efficiency measurements as well as monitoring the global cell performance especially the fill factor of the solar cell. The results are substantially the same as those obtained with cells deposited in multi-chamber reactors.
  • Furthermore, an oxygen peak can be observed with a SIMS analysis at the treated p-i interface, meaning that the above described treatment has been used. Typically, the amount of oxygen in the peak is higher than 1019 atoms.cm3.
  • According to a second embodiment of the invention, after the deposition of the p-layer and before the deposition of the i-layer, the internal surfaces of the reactor are dosed with a vapour or gas comprising ammonia, hydrazine or volatile organic amines. This dosing operation is performed at low pressure conditions (0.05 to 100 hPa), between 100 and 350°C, typically at around 200°C and during less than 10 minutes, typically around to 2 minutes. The flow of gas has to be sufficient. For example, 90 hPa.sec is a good value for ammonia. After the dosing operation, a short pumping period of less than 5 minutes is also respected before the deposition of the i-layer.
  • A nitrogen peak can be observed with a SIMS analysis at the treated n-i interface, meaning that such a treatment has been used. Typically, the amount of nitrogen is higher than 1019 atoms.cm-3.
  • For both embodiments of the invention, it may be useful to deposit on the p-layer, after the above described treatments, a hydrogen-diluted buffer layer. This layer is obtained by PECVD of a mix of 10% silane and 90% hydrogen. The plasma excitation frequency used is 40.68 MHz, the temperature is 200°C, while the pressure is kept at 0.5 hPa and the power RF is applied at a level of 60 W. Such a layer alone has usually already a beneficial effect on the boron cross contamination in the i-layer.
  • The method of the invention, according to both described embodiments, offers the advantage to eliminate the boron contamination while working with a single reactor. There is neither wasted pumping time nor loss of time due to transfer of the substrate out of the reactor for a cleaning step nor loss of time for reheating of the substrate which cooled down during the transfer. Moreover, apart from simpler and faster processes the single chamber approach bears the potential of considerably simplified deposition systems as compared to multi-chamber systems. It has to be noted that such methods allow to produce a complete solar cell in only 30 minutes.
  • A person skilled in the art can easily adapt the above described treatments to a n-i-p solar cell in order to avoid phosphorus cross-contamination after the deposition of n-doped layer.
  • Needless to say that the invention can also be applied to any junction based on a p-doped or n-doped layer. The dosing can also be performed by injecting the dosing compound directly in the gas feeding line.

Claims (6)

  1. A method for producing a semiconducting device comprising at least a layer doped with a doping agent and a layer of another type deposited on said doped layer in a single reaction chamber, wherein the deposition steps of said layers are separated by an operation for avoiding the contamination by the doping agent of said another layer, said operation comprising a dosing of the reaction chamber with a vapour or gas comprising water, methanol, isopropanol or another alcohol, or with a vapour or gas comprising ammonia, hydrazine or volatile organic amines able to react with the doping agent.
  2. The method of claim 1, wherein said dosing is performed at from 0.05 to 100 hPa and between 100 and 350°C for less than 10 minutes.
  3. The method of claims 1 to 2, wherein the doped layer is a p-doped layer.
  4. The method of claims 1 to 2, wherein the doped layer is a n-doped layer.
  5. The method of claim 3, wherein said operation is followed by the deposition of a buffer layer on the p-layer.
  6. The method of any of claims 1 to 5, wherein said dosing is followed by a pumping at high vacuum and between 100 and 350°C for less than 5 minutes.
EP03750232.5A 2002-10-25 2003-10-22 Method for producing semiconducting devices Expired - Lifetime EP1554413B1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US42117102P 2002-10-25 2002-10-25
US421171P 2002-10-25
US43976403P 2003-01-13 2003-01-13
US439764P 2003-01-13
US47667003P 2003-06-06 2003-06-06
US476670P 2003-06-06
PCT/CH2003/000685 WO2004038774A2 (en) 2002-10-25 2003-10-22 Method for producing semi-conducting devices and devices obtained with this method

Publications (2)

Publication Number Publication Date
EP1554413A2 EP1554413A2 (en) 2005-07-20
EP1554413B1 true EP1554413B1 (en) 2013-07-24

Family

ID=32180507

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03750232.5A Expired - Lifetime EP1554413B1 (en) 2002-10-25 2003-10-22 Method for producing semiconducting devices

Country Status (6)

Country Link
US (3) US7344909B2 (en)
EP (1) EP1554413B1 (en)
JP (1) JP4733519B2 (en)
KR (1) KR101015161B1 (en)
AU (1) AU2003269667A1 (en)
WO (1) WO2004038774A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013202366B4 (en) * 2012-02-28 2021-04-01 Bay Zu Precision Co., Ltd Single-chamber process for manufacturing a photovoltaic unit

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004003761A1 (en) * 2004-01-23 2005-08-25 Forschungszentrum Jülich GmbH Production method for silicon solar cells comprising μc silicon layers
TWI375083B (en) * 2006-09-12 2012-10-21 Mutual Tek Ind Co Ltd Light emitting apparatus and method for the same
KR101046520B1 (en) 2007-09-07 2011-07-04 어플라이드 머티어리얼스, 인코포레이티드 Source gas flow path control in pecvd system to control a by-product film deposition on inside chamber
US20110180142A1 (en) * 2008-08-19 2011-07-28 Oerlikon Solar Ag, Truebbach Electrical and optical properties of silicon solar cells
US8652871B2 (en) * 2008-08-29 2014-02-18 Tel Solar Ag Method for depositing an amorphous silicon film for photovoltaic devices with reduced light-induced degradation for improved stabilized performance
DE102009051347A1 (en) * 2009-10-30 2011-05-12 Sunfilm Ag Process for producing semiconductor layers
EP2517267A2 (en) 2009-12-22 2012-10-31 Oerlikon Solar AG, Trübbach Thin-film silicon tandem solar cell and method for manufacturing the same
DE102010013039A1 (en) * 2010-03-26 2011-09-29 Sunfilm Ag Method for manufacture of photovoltaic cell, involves forming intrinsic layer between two conductive layers of different conductance, and separating one of conductive layers and one portion of intrinsic layer in separation chamber
CN103262263A (en) 2010-09-03 2013-08-21 东电电子太阳能股份公司 Method for thin film silicon photovoltaic cell production
US8927857B2 (en) 2011-02-28 2015-01-06 International Business Machines Corporation Silicon: hydrogen photovoltaic devices, such as solar cells, having reduced light induced degradation and method of making such devices
JP2013191770A (en) * 2012-03-14 2013-09-26 Tokyo Electron Ltd Method for stabilizing film formation device and film formation device

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4398054A (en) * 1982-04-12 1983-08-09 Chevron Research Company Compensated amorphous silicon solar cell incorporating an insulating layer
US4547621A (en) * 1984-06-25 1985-10-15 Sovonics Solar Systems Stable photovoltaic devices and method of producing same
US5512102A (en) * 1985-10-14 1996-04-30 Semiconductor Energy Laboratory Co., Ltd. Microwave enhanced CVD system under magnetic field
CA1321660C (en) * 1985-11-05 1993-08-24 Hideo Yamagishi Amorphous-containing semiconductor device with high resistivity interlayer or with highly doped interlayer
US4682407A (en) * 1986-01-21 1987-07-28 Motorola, Inc. Means and method for stabilizing polycrystalline semiconductor layers
JPS62232173A (en) * 1986-04-01 1987-10-12 Toa Nenryo Kogyo Kk Amorphous silicon solar cell
US4845043A (en) * 1987-04-23 1989-07-04 Catalano Anthony W Method for fabricating photovoltaic device having improved short wavelength photoresponse
US4914046A (en) * 1989-02-03 1990-04-03 Motorola, Inc. Polycrystalline silicon device electrode and method
AU632241B2 (en) * 1990-09-06 1992-12-17 Mitsui Toatsu Chemicals Inc. Amorphous silicon solar cell and method for manufacturing the same
US5256887A (en) * 1991-07-19 1993-10-26 Solarex Corporation Photovoltaic device including a boron doping profile in an i-type layer
US5307186A (en) * 1991-08-09 1994-04-26 Sharp Kabushiki Kaisha Liquid crystal light valve having capability of providing high-contrast image
JP2733176B2 (en) * 1992-11-16 1998-03-30 キヤノン株式会社 Photovoltaic element and power generation device using the same
JP3590416B2 (en) 1993-11-29 2004-11-17 アネルバ株式会社 Thin film forming method and thin film forming apparatus
EP0661731B1 (en) 1993-12-28 2000-05-31 Applied Materials, Inc. A single chamber CVD process for thin film transistors
JPH0855838A (en) * 1994-08-12 1996-02-27 Sony Corp Cleaning method for microfabrication equipment
US6020035A (en) 1996-10-29 2000-02-01 Applied Materials, Inc. Film to tie up loose fluorine in the chamber after a clean process
EP0844649A3 (en) 1996-11-20 1999-10-06 Nec Corporation A method for boron contamination reduction in IC fabrication
DE19706783A1 (en) 1997-02-20 1998-08-27 Siemens Ag Methods for producing doped polysilicon layers and layer structures and methods for structuring layers and layer structures which comprise polysilicon layers
US6479373B2 (en) 1997-02-20 2002-11-12 Infineon Technologies Ag Method of structuring layers with a polysilicon layer and an overlying metal or metal silicide layer using a three step etching process with fluorine, chlorine, bromine containing gases
JPH11140675A (en) * 1997-11-14 1999-05-25 Sony Corp How to clean the vacuum chamber
JP3481123B2 (en) * 1998-03-25 2003-12-22 三洋電機株式会社 Photovoltaic device
EP0949688A1 (en) * 1998-03-31 1999-10-13 Phototronics Solartechnik GmbH Thin film solar cell, method of manufacturing the same, and apparatus for carrying out the method of manufacturing
US6261862B1 (en) * 1998-07-24 2001-07-17 Canon Kabushiki Kaisha Process for producing photovoltaic element
US6204192B1 (en) * 1999-03-29 2001-03-20 Lsi Logic Corporation Plasma cleaning process for openings formed in at least one low dielectric constant insulation layer over copper metallization in integrated circuit structures
JP3672471B2 (en) * 1999-12-28 2005-07-20 シャープ株式会社 Method for manufacturing photoelectric conversion element
DE60039875D1 (en) * 1999-06-25 2008-09-25 Massachusetts Inst Technology CYCLIC THERMAL HEALING METHOD FOR REDUCING CRYSTAL TRANSLATION
JP3088721B1 (en) * 1999-08-11 2000-09-18 キヤノン販売株式会社 Impurity processing apparatus and cleaning method for impurity processing apparatus
JP2001093889A (en) * 1999-09-27 2001-04-06 Matsushita Electric Ind Co Ltd Plasma cleaning method and wet cleaning method
JP2002305315A (en) * 2001-01-31 2002-10-18 Canon Inc Method of forming semiconductor device and semiconductor device
KR100447284B1 (en) * 2002-07-19 2004-09-07 삼성전자주식회사 Method of cleaning chemical vapor deposition chamber
US20040018715A1 (en) * 2002-07-25 2004-01-29 Applied Materials, Inc. Method of cleaning a surface of a material layer
JP3866694B2 (en) * 2003-07-30 2007-01-10 株式会社日立ハイテクノロジーズ LSI device etching method and apparatus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013202366B4 (en) * 2012-02-28 2021-04-01 Bay Zu Precision Co., Ltd Single-chamber process for manufacturing a photovoltaic unit

Also Published As

Publication number Publication date
US7344909B2 (en) 2008-03-18
KR101015161B1 (en) 2011-02-16
WO2004038774A2 (en) 2004-05-06
US20090127673A1 (en) 2009-05-21
JP4733519B2 (en) 2011-07-27
KR20050060097A (en) 2005-06-21
US7504279B2 (en) 2009-03-17
JP2006504283A (en) 2006-02-02
US20080076237A1 (en) 2008-03-27
WO2004038774A3 (en) 2004-09-10
AU2003269667A8 (en) 2004-05-13
EP1554413A2 (en) 2005-07-20
AU2003269667A1 (en) 2004-05-13
US20040135221A1 (en) 2004-07-15

Similar Documents

Publication Publication Date Title
US7504279B2 (en) Method for producing semi-conducting devices and devices obtained with this method
US7582515B2 (en) Multi-junction solar cells and methods and apparatuses for forming the same
US7919398B2 (en) Microcrystalline silicon deposition for thin film solar applications
US20080173350A1 (en) Multi-junction solar cells and methods and apparatuses for forming the same
US7741144B2 (en) Plasma treatment between deposition processes
US20080271675A1 (en) Method of forming thin film solar cells
WO2010005439A1 (en) Solar cells and methods and apparatuses for forming the same
US20080223440A1 (en) Multi-junction solar cells and methods and apparatuses for forming the same
US20130112264A1 (en) Methods for forming a doped amorphous silicon oxide layer for solar cell devices
US20120145185A1 (en) Method for cleaning the surface of a silicon substrate
US20090208668A1 (en) Formation of clean interfacial thin film solar cells
US20090130827A1 (en) Intrinsic amorphous silicon layer
US7927907B2 (en) Method of making silicon solar cells containing μC silicon layers
US20110171774A1 (en) Cleaning optimization of pecvd solar films
CN100513637C (en) Method for producing semi-conducting devices and devices obtained with this method
US8628999B2 (en) Solar cell made in a single processing chamber
EP2304072A1 (en) Solar cells and methods and apparatuses for forming the same

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050317

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: BUCHER, CEDRIC

Inventor name: POPPELLER, MARKUS

Inventor name: HOWLING, ALAN

Inventor name: HOLLENSTEIN, CHRISTOPH

Inventor name: KROLL, ULRICH

Inventor name: SCHMITT, JACQUES

Inventor name: BALLUTAUD, JULIETTE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OC OERLIKON BALZERS SA

17Q First examination report despatched

Effective date: 20090407

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OERLIKON TRADING AG, TRUEBBACH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: OERLIKON SOLAR AG, TRUEBBACH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 60344575

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0016440000

Ipc: H01L0021205000

RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 31/0288 20060101ALI20121112BHEP

Ipc: H01L 21/02 20060101ALI20121112BHEP

Ipc: H01L 31/075 20120101ALI20121112BHEP

Ipc: H01L 31/18 20060101ALI20121112BHEP

Ipc: H01L 21/22 20060101ALI20121112BHEP

Ipc: H01L 31/20 20060101ALI20121112BHEP

Ipc: C23C 16/44 20060101ALI20121112BHEP

Ipc: H01L 21/205 20060101AFI20121112BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TEL SOLAR AG

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 623860

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60344575

Country of ref document: DE

Effective date: 20130912

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 623860

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130724

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130724

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130703

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131024

26N No opposition filed

Effective date: 20140425

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131024

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140630

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60344575

Country of ref document: DE

Effective date: 20140425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20031022

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130724

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20151013

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60344575

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170503